Synthetic polymers from sulfo-bis(aminoalkyl)fluorene

ABSTRACT

Polyamides containing sulphofluorene links to accept basic dyestuffs (not acid) for single stage pattern dyeing.

United States Patent Lodge 1 Aug. 29, 1972 [54] SYNTHETIC POLYMERS FROMSULFO-BIS(AMINOALKYL)FLUORENE [72] Inventor: John Ewart Lodge, ICIFibres Limited, Pontypool, England [22] Filed: July 7, 1970 [21] Appl.No.: 60,999

Related US. Application Data [62] Division of Ser. No. 702,784, Feb. 5,1968.

[30] Foreign Application Priority Data Feb. 13, 1967 Great Britain..6,767/67 52 us. 01. ..260/78 R, 8/55, 57/140 R, 260/292 N, 260/78 A,260/78 L 51 1111. C1. ..C08g 20/20 [58] Field of Search ..260/78 RKorshak-Frunze: Synthetic Hetero-Chain Polyamides, 1964, pp. 223- 224Primary Examinerl-Iarold D. Anderson Attorney-Cushman, Darby & Cushman[57] ABSTRACT Polyamides containing sulphofluorene links to accept basicdyestuffs (not acid) for single stage pattern dyeing.

8 Claims, No Drawings SYNTHETIC POLYMERS FROM SULFO-BIS(AMINOALKYL)FLUORENE This is a division of my copending application,Ser. No. 702,784, filed Feb. 5, 1968.

This invention relates to the manufacture of synthetic linear polymersand more particularly to synthetic linear copolyamides containingfluorene sulphonic acid residue in the carbon chain, and to shapedarticles made therefrom.

l-ligh molecular weight synthetic linear polyamides, by which is meantpolyamides of sufficiently high molecular weight to be capable of beingmelt spun, have long been known and some are manufactured on a largescale for melt-spinning into filaments by the polycondensation of lowmolecular weight diamines and dicarboxylic acids or of amino-carboxylicacids. For example, polyhexamethylene adinamide may be made by thecondensation of hexamethylene diamine and adipic acid. A similarpolyamide is obtainable by the polycondensation of omega-amino-caproicacid. In place of the latter the corresponding lactam, namelyepsilon-caprolactam can be polymerized so as to afford a polyamide.

Such polyamides e.g. polyhexarnethylene adipamide, may be melt-spun intofilaments having many attractive textile properties including a hightenacity and resistance to abrasion. The filaments are commonly dyed byacid dyestuffs but basic dyestuffs can also be used though in the caseof the latter is is desirable to select those possessing good fastnessto light.

Much attention has been paid particularly in recent years to the problemof modifying polyamides so as to increase or decrease their dyeability,i.e., the depth of shade obtained with a given dyestuff under givenconditions. The reason for the interest in this problem is as follows.If a fabric is knitted or woven or otherwise fabricated of two or morepolyamides of different dyeabilities, a pattern can immediately beobtained by a single dyeing operation, which constitutes an attractivecommercial proposition.

Whilst polyamides can be modified for the above purpose by the physicalapplication or incorporation of suitable agents it is preferable thatthe latter be built into the polyamide chain, i.e., chemically combinedtherewith, because more permanent effects are thereby obtained. Forexample, if bifunctional compounds capable of taking part in thepolyamide polycondensation and bearing, say, sulphonic acid groups, areincluded in the starting materials used in the manufacture of thepolyamide they will form part of the linear polyamide chain and theadditional sulphonic acid groups will increase the dyeability of theresulting polyamide with respect to basic dyestuffs whilst reducing theuptake of acid dyestuffs. Suitable bifunctional compounds for takingpart in the aforesaid condensation reaction have, for instance, aplurality (especially two) or amino and/or carboxyl groups. Thusdiarnino aromatic sulphonates can be used to give polyamides dyeing moredeeply with basic dyestuffs.

It has now been found that metal salts of the hitherto undisclosedsulpho-bis 9, 9-aminoalkylfluorenes are very useful for this purpose.The alkyl group may be gamma-amino-n-propyl, methyl, ethyl, isobutyl orstearyl. Instead of the amino groups functionally equivalent groups,e.g. the formylamino group may be employed.

Accordingly, therefore, from one aspect the present invention provides,as novel compounds, sulpho 9, 9- bis-aminoalkylfluorenes.

The metal salts are of monovalent metals e.g. sodium, potassium or ofbasic organic salts of a divalent metal e.g. calcium benzoate, calciumacetate, zinc acetate, strontium formate and stannous valerate.

According to another aspect the invention provides monovalent metal orbasic organic divalent metal salts of the sulpho-9, 9-bisaminoalkylfluorene compounds referred to above.

Examples of the sulpho-bis aminoalkylfluorenes of this invention aredisodium 9, 9-bis-beta-aminoethylfluorene-Z, 7-

disulphonate sodium 9,-bis-beta-aminoethylfluorene-2-sulphonatepotassium 9,9-bis-beta-aminoethylfluorene-2- sulphonate lithium9,9-bis-gamma-aminopropylfluorene-2- sulphonate sodium9,-9-bis-delta-aminobutylfluorene -2- sulphonate2-bensoyloxybariumsulpho-9,9-bis-beta-aminoethylfluorene 2,7-bis-acetoxybariumsulpho-9,9-bis-betaaminoethylfluorene2,7-bis-hexanoyloxymagnesiumsulpho-9,9-bis-deltaarninobutylfluoreneAccording to a further aspect the present invention providesfilament-forming synthetic linear copolyamides consisting essentially ofthe polymeric condensation product of an equi-molecular mixture of analiphatic alpha omega-diamine or cylco aliphatic diamine having fromfour to 20 carbon atoms and an aliphatic alpha, omega-dicarboxylic acidhaving from six to 22 carbon atoms, and/or an aliphaticomegaaminocarboxylic acid containing from five to 21 carbon atoms, orpolyamide forming functional equivalents thereof and a9,9-bis-omega-aminoalkylfluorene mono or di-sulphonic acid or apolyamideforming functional derivative thereof together withapproximately an equal molecular proportion of an aliphatic alpha,omega-dicarboxylic acid having from six to 22 carbon atoms, the saidfluorene derivative being present in a molecular proportion with respectto the foregoing acids of from one-fourth to 10 percent.

The fluorene intermediate may be added the reagents or melt before,during or after the polyamide polymerization of polycondensation andshould be employed in a molecular proportion not exceeding 10 percent sothat not more than 10 percent of the repeating amide units containfluorene nuclei. In other words the number of moles of the fluoreneintermediate used must not exceed one-tenth the number of moles ofdicarboxylic acid or arnino-carboxylic acid employed in making thepolyamide. Not less than one-fourth mol. percent of the fluorenecompound should be used and the preferred proportion is one-half to 5mol. percent.

According to yet a further aspect, therefore, this invention comprises aprocess for the manufacture of synthetic linear copolyamides by heating,to effect polymerization, an approximately, equimolecular mixture of analiphatic alpha, omega-diamine or cyclo aliphatic diamine having fromfour to 20 carbon atoms and an aliphatic alpha, omega-dicarboxylic acidhaving from six to 22 carbon atoms, and/or an aliphaticomega-aminocarboxylic acid containing from five to 21 carbon atoms, orinstead of said monomer a polyamideforming functional equivalent thereoftogether with a molecular proportion with respect to the foregoing acidsof from one-fourth to percent of the monovalent metal or divalent basicorganic salt of a 9,9-bis-omega-aminoa1ky1fluorene monoor disulphonicacid or a polyamide-forming functional derivative thereof, added at anystage of the polymerization and accompanied by approximately the samemolecular quantity of an aliphatic alpha, omegadicarboxylic acid fromsix to twenty-two carbon atoms.

Examples of the aliphatic diamines and cycloaliphatic diamines are:

Hexamethylene diamine 3-methylhexamethylene diamine Tetramethylenediamine Decamethylene diamine Octamethylene diamine l:6-diamino-6-methylheptane Bis (p-aminocyclohexyl) methane Examples ofthe aliphatic dicarboxylic acids are:-

Adipic acid Beta-methyladipic acid I Sebacic acid Pimelic acidHexadecamethylene dicarboxylic acid Suitablesulpho-bis-aminoalkylfluorenes are those hereinbefore referred to.

In place of the approximately equi-molecular mixture of the aliphaticdiamine and dicarboxylic acid, there may conveniently be employedpolyamide-forming functional derivatives such as the diamine-dicaroxylicacid salt derived therefrom, e.g. hexamethylene diammonium adipate(derived from hexamethylene diamine and adipic acid). Thus, forinstance, a copolyamide according to the invention may be made byheating together 78.6 parts by weight of hexamethylene diammoniumadipate and 3.2 part by weight of sodium9,9-bis-beta-ammoniumethylfluorene-2-sulphonate adipate (i.e. 2 molarpercent). As already mentioned the starting materials used in making thepresent copolyamides may be brought together in any desired order. Ifthe salts are employed, as just mentioned, the fluorene salt can beadded to the hexamethylene diammonium adipate and the two heatedtogether either in an autoclave or a continuous polymerization apparatusin order to effect polymerisation, or the fluorene salt can be added tothe reaction mixture during the polymerization of the hexamethylenediammonium adipate; alternatively the two salts can be polymerizedseparately by heating, and the resulting polyamides then heated togetherin order to bring about amide interchange and thus produce the requiredcopolyarnide. Thus a copolyamide can be made by (l) first polymerisinge.g. over 10 percent of the fluorene salt monomer with, say,hexamethylene diammonium adipate, (2diammonium separately polymerising afurther proportion of hexamethylene diammonium adipate to producepolyhexamethylene adipamide and (3) heating the two polymers together toeffect interaction (amide interchange) whereby a copolyamide is obtainedsimilar to that which would have resulted if all the hexamethylenediammoninium adipate had been heated with the fluorene salt monomer inone polymerization Other salts which may be used in conjunction with thelatter starting material are: hexamethylene diammonium sebacateOctamethylene diammonium adipate Pentarnethylene diammonium sebacateDodecamethylene diammonium adipate If desired, the diamenes may be usedin the form of their N-formyl derivatives or other functionalpolyamide-forming derivatives; also the acids may be employed in theform of their ethyl esters for example.

Likewise instead of the amino-carboxylic acids the chemically equivalentlactams derived therefrom may be employed. Examples of suitableamino-carboxylic acids and lactams are:

Epsilon-aminocaproic acid Epsilon-caprolactam Omega-aminoundecanoic acidOmega-aminoheptanoic acid More than one of the aforesaid startingmaterials, namely, diamines, dicarboxylic acids or amino-carobxylicacids or their chemical equivalents, may be employed.

Amongst the reagents employed in making the present polyamides there maybe included monofunctional compounds in small quantity, notablymonoamines or monobasic acids, e.g. acetic acid, in order to preventpolymerization proceeding beyond the desired degree at elevatedtemperatures, for example, when the polyamide is held molten for thepurpose of meltspinning it into filaments. Such monofunctional compoundsare known as viscosity stabilizers. In the case of the manufacture of apolyamide from a diamine and a dicarboxylic it is also possible tocontrol the degree of polymerization by employing a suitable excess ofthe diamine or of the dicarboxylic acid. Other adjuvants may also beincorporated in the polyamides at any convenient stage of theirmanufacture for instance: Dystuffs, pigments, dystuff-formers,plasticizers lustrants, resins.

In the following examples which are by way of illustrating not limitingthe invention the parts are parts by weight.

EXAMPLE 1 200 parts of 9,9-di(3'-aminopropyl)-fluorene dihydrochlorideare added during 1 hour with stirring to 375 parts of 98 percentsulphuric acid. The solution obtained is stirred at 100C. for 4 hours,and then poured into 1,000 parts of methanol. The white precipitate of9,9-di(3'-aminopropyl)-fluorene 2,7- disulphonic acid is filtered offand washed with methanol until free of sulphuric acid. Found: S: 14.5%;N: 6.3%; C H N S 0 requires S: 14.54%; N: 6.36%.

EXAMPLE 2 132.8 parts of 9,9-di-(3-aminopropyl)-fluorene-2,7-disulphonic acid and 24.14 parts of sodium hydroxide are dissolved in1,000 parts of water, and the solution added to an autoclave containing8,000 parts of hexamethylene diammonium adipate, 44.1 parts of adipicacid 9.16 parts of acetic acid and 20.7 parts of titanium dioxide. Themixture is stirred and heated to 205C. during 1 hour reaching a pressureof 250-1b./sq. in. The temperature is then raised to 240C. during 1 hourwhilst the pressure is maintained (by a spring-loaded escape valve).During the next (third) hour the pressure is allowed to fall to oneatmosphere while the temperature is raised further to 275C; the polymeris finally heated at 285C. for 35 minutes.

The resulting white polymer which possesses a Relative Viscosity of 33.4is melt-spun under steam to give a yarn of 20 filaments. The latter aredrawn to 3.66 times their original length and then have a total denierof 70 and 30 percent extensibility at break.

The Relative Viscosity is determined by dividing the viscosity of an 8.4percent w/w solution of the polymer in 90 percent w/w aqueous formicacid at 25 C. by the viscosity of the said aqueous formic acid at thesame temperature.

The yarn on analysis proved to have 49 cm. eqts. of amine ends and 71gm. eqts. of carboxyl ends per million gms; the relative viscosity is34.5.

A hank of yarn is immersed for 3 hours in 200 times it weight of a 0.05percent aqueous solution of Acid Blue No. 45 containing 1 percent ofacetic acid, but is hardly stained. The amount of dyestuff taken up,equivalent dye uptake (E.D.U.), is measured by dissolving 50 mg. of theyarn in 20 ml. of 40 percent sulphuric acid and measuring the opticaldensity at430 my. in a Unicam SP. 600 spetrophotometer. The dyestufftaken up by polyhexamethylene adipamide yarn under the same conditionsis 30 times as much.

At a pH of 5.6 the yarn possessed an E.D.U. of Basic Orange 28 (ColorIndex) 5.22 times that of polyhexamethylene adipamide yarn whilst at pH7.0 the E.D.U. was 3.23 times that of polyhexamethylene adipamide yarn.

EXAMPLE 3 7930 parts of caprolactam, a solution of 154.7 parts of9,9-di(3-aminopropyl)-fluorene-2, 7-disulphonic acid 28.12 parts ofsodium hydroxide in 3 liters of water, and 51.32 parts of adipic acid isadded to an autoclave under an atmosphere of nitrogen. The temperatureis raised during 1 hour to 220C. and the steam pressure to 250 psig;during the next hour the temperature is raised to 270C. and steamallowed to escape slowly reducing the pressure to 180 psig; whilstduring the next hour the temperature is raised to 285C. and the pressureallowed to fall to atmospheric. The molten polymer is held to 285C. for45 minutes under an atmosphere of steam before being extruded into aribbon.

The resulting polymer has a Relative Viscosity of 30.1, an amine endgroup of 5 l .6 g./ g. and a carboxyl end group content of 54 g./10 g.

This polymer is spun at 270C. to a 20 filament yarn of 400 denier. Theyarn, after drawing at a draw ratio of 3.31, has a denier of 114 and anextension at break of 40 percent.

At a pH of 3.7 the yarn possesses an E.D.U. of Acid Blue 45 (ColorIndex) of one-sixtieth of that of a polycaproamide yarn under similarconditions. At a pH of 3.0 the E.D.U. of the yarn to Basic Orange 28(Color Index) was 12.5 times that of the polycaproamide yarn.

EXAMPLE 4 7,543 parts of hexamethalyne diammonium dodecamethylenedioate, a solution of 96 parts of 9, 9-

iiifiilif is ill iiifiififiielfiiii ifi wiii 22 31.84 parts of adipicacid is added to an autoclave, under an atmosphere of nitrogen.Polymerization is effected as described in Example 3 to produce a whitepolymer having an amine end group content of 65.2 g./ 10 g. and acarboxyl content of 54 g./ 1 D g.

This polymer is melt spun under an atmosphere of steam at 270C. to a 20filament yarn of 260 denier. After drawing at a draw ratio of 3.3 theyarn has a denier of 74.5 and an extension at break of 19 percent.

At a pH of 3.7 the yarn possesses an E.D.U. of Acid Blue 45 (ColorIndex) one twenty-eighth of polyhexamethylene dodecamethylene diarnide.At a pH of 3.0 the E.D.U. of the yarn to Basic Orange 28 (Color Index)is nine times that of the polyhexamethylene dodecarnethylene diamideyarn.

What I claim is:

1. A synthetic linear filament-forming copolyamide consistingessentially of the polymeric condensation product of an equimolarmixture of an aliphatic alpha omega-diamine or cycloaliphatic diaminehaving from four to 20 carbon atoms and an aliphatic alpha,omegadicarboxylic acid having from six to 22 carbon atoms, and/or analiphatic omega-amino-carboxylic acid containing from five to 21 carbonatoms, or polyamideforming functional equivalents thereof, and a9,9-bisomega-aminoalkylfluorene mono or disulphonic acid or apolyamide-forming functional derivative thereof together with anequimolecular proportion of an aliphatic alphaomega-dicarboxylic acidhaving from six to 22 carbon atoms, said fluorene derivative beingpresent in a molecular proportion of from one-fourth to 10 percent withrespect to the foregoing acids.

2. A copolyamide according to claim 1 wherein the fluorene derivative ispresent in a molecular proportion of from one-half to 5 percent.

3. A copolyamide according to claim 1 wherein the fluorene dicarboxylicacid is in the form of a salt of a monovalent metal selected from thegroup consisting of sodium and potassium or of a salt of basic organicdivalent metal selected from the group consisting of calcium benzoate,calcium acetate, zinc acetate, strontium formate and stannous valerate.

4. A copolyamide according to claim 3 wherein the monovalent 5. Acopolyamide according to claim 3 wherein the basic metal is sodium orpotassium. divalent metal is calcium benzoate, calcium acetate, zincacetate, strontium formate or stannous valerate.

6. A copolyamide according to claim 1 wherein the first mentioneddiamine is hexamethylene diamine and the dicarboxylic acid adipic acidor alpha-omegadodecamethylene dicarboxylic acid.

7. A polyamide according to claim 1 wherein the omega-aminocarboxylicacid polyamide-forming functional derivative is caprolactam.

8. A copolyamide according to claim 1 wherein the9,9-ibs-omega-aminoalkylfluorene sulphonic acid is9,9-bis-gamma-amino-n-propyl fluorene 2,7- disulphonic acid.

2. A copolyamide according to claim 1 wherein the fluorene derivative ispresent in a molecular proportion of from one-half to 5 percent.
 3. Acopolyamide according to claim 1 wherein the fluorene dicarboxylic acidis in the form of a salt of a monovalent metal selected from the groupconsisting of sodium and potassium or of a salt of basic organicdivalent metal selected from the group consisting of calcium benzoate,calcium acetate, zinc acetate, strontium formate and stannous valerate.4. A copolyamide according to claim 3 wherein the monovalent metal issodium or potassium.
 5. A copolyamide according to claim 3 wherein thebasic organic divalent metal is calcium benzoate, calcium acetate, zincacetate, strontium formate or stannous valerate.
 6. A copolyamideaccording to claim 1 wherein the first mentioned diamine ishexamethylene diamine and tHe dicarboxylic acid adipic acid oralpha-omega-dodecamethylene dicarboxylic acid.
 7. A polyamide accordingto claim 1 wherein the omega-aminocarboxylic acid polyamide-formingfunctional derivative is caprolactam.
 8. A copolyamide according toclaim 1 wherein the 9,9-bis-omega-aminoalkylfluorene sulphonic acid is9,9-bis-gamma-amino-n-propyl fluorene 2,7-disulphonic acid.